Cosmetic products containing milk constituents

ABSTRACT

A cosmetic or soap product containing natural milk proteins in the form of micelles formed by the addition of calcium to an aqueous solution of casein. These micelles give the product light reflection properties analogous to those produced by the addition of a natural milk.

The subject of the present invention is cosmetic and/or soap productscontaining substances of milk origin, that is to say ingredients derivedfrom whole or skimmed milk or extracts from milk. The invention is alsoconcerned with the preparation of such products.

The favourable effect of milk or products derived from milk on cosmeticcompositions, such as lotions for the skin, hair lotions, shampoos,softening creams, and soaps, is well known, and numerous compositionscontaining such ingredients have been described in the state of the art.

Thus, the document U.S. Pat. No. 3,959,491 describes cosmetic creams andlotions containing sterilized milk and milk cream. To improve thepreservation of such products in storage, this document recommendsincorporating into the cosmetic compositions saturated fatty acids,triglyceride esters of saturated fatty acids, stabilising aliphaticdiols, sequestering agents and biocidal agents, in particular enzymedenaturants and bactericides. Of course, apart from the preservationagents above, the cosmetics described in this document contain the usualconstituents of cosmetics, including perfumes, opacifiers and others.

The document DD-A-112,351 (East Germany) describes cosmetic productscontaining an active complex derived from milk or whey constituents, inparticular non-denatured proteins, vitamins and constituent salts ofmilk. According to a process for preparation of such an active complexas described in this document, a mass of whey is subjected toconcentration under reduced pressure followed by centrifuging and,finally, drying by atomization. For the manufacture of cosmetics,proportions of the order of 10-20% of the active complex such asprepared as described are added to the cosmetics.

The document U.S. Pat. No. 4,460,571 describes a cosmetic on a base ofwhole or powdered milk which particularly lends itself to topodermic andcapillary uses. In this, there are in question fluid compositions,antiseptic and perfumed compositions containing skimmed milk ornon-skimmed milk, or containing dissolved powdered milk, and, apart fromwater and the usual ingredients of such lotions, quite a high proportionof alcohol.

The document GB-A-2,056,854 describes cosmetics, in particular lotionsand shampoos, containing, apart from the normal ingredients inherent insuch products, very high proportions of milk (40-80%) and, as astabilising agent, propylene glycol.

The document GB-A-2,051,076 describes a process for preparation ofmoisturizing agents useful in the field of cosmetics, these agents beingderived by fermentation from skimmed milk.

More precisely, this document describes the formation of water solublecasein hydrolysates by the action of lactic ferments and proteases.These hydrolysates, colourless and transparent, are then incorporated,at levels of 0.1 to 10% by weight, into cosmetics, in particularsoftening lotions for the skin, creams, and soapstuff products, etc., insuch a manner as to confer, on these cosmetics, improved properties inrespect of softening power, prevention of drying out of the skin, andmaintaining its elasticity.

The document GB-A-2,037,160 describes a lyophilised product derived frommilk having advantagous cosmetic properties, in particular formoisturizing and softening of the skin along with its regeneration. Sucha product contains principally lactose, milk proteins, and water. It isobtained by fermentation of skimmed milk or non-skimmed milk by means ofenzymes and milk ferments, in particular pancreatin, pepsin, and theferments Lactobacillus bulgaricus and Streptococcus thermopilus. Thefermented product is then lyophilised and used, in a mixture, withcosmetic compositions to improve their properties.

The document DE-A-2,623,250 describes cosmetic compositions containingmilk. Among these, there are mentioned shampoos, beauty lotions, shavingcreams, creams for the skin, etc. All these products have in common,apart from milk and water, surfactant substances, such asalkyl-sulphonates, sulphonated fatty acids, and the salts of tertiaryamines, etc. The milk may be present in the form of whole milk, low fatmilk, acidified milk, skimmed milk, yogurt, cream, etc. in aqueous formor in a powder. Furthermore, the compositions described may alsocontain, depending on the use for which they are intended, otheringredients such as lanolin, perfumes, glycerine and other similarproducts.

The document DE-A-2,650,560 describes cosmetic compositions containingmilk in the form of yogurt, this being usable in the fresh state or in apowder. Among such cosmetics, the document mentions liquid and solidproducts, in particular beauty milks, creams, and aerosols for foams.These compositions contain, apart from yogurt, preserving agents,antioxidants, cheletors, and protease inhibitors.

The document EP-A-46,326 discloses cosmetic compositions applicable tothe skin or the hair containing casein in the form of milk or other milkproteins and, more particularly, in the form of whey. These ingredientsderived from milk include whey, lactose-free whey, and demineralisedwhey, and their concentrates prepared by chemical or physical processes,also including the precipitate resulting from neutralisation of thewhey, calcium enriched whey, and derivatives of whey resulting fromseparation of the above-mentioned substances.

Among the cosmetics capable of being improved by the ingredients derivedfrom whey, this document mentions products for care of the skin and thehair, in particular shampoos, dressings, hair lotions, conditioningproducts, products for permanent waves, dyes, decolourants, bodylotions, cold cream, cleansing creams, emollients, detergents, soaps,make-up products, lipsticks, shaving products, sun protecting products,screening products, and depilatories, etc.

In general, for the formulation of such modified cosmetics, there areadded to the mixture of the ingredients of the cosmetics, theabove-mentioned derivatives of whey, either in the form of aqueoussolutions, or in solid form. To ensure the preservation of suchcosmetics, the document recommends the addition of inhibiting agents orgermicides.

Even though the cosmetics described in the previous art described aboveshow, after modification, by the contribution of milk or of milkderivatives, interesting new properties and undeniable improvements,they are not however without certain disadvantages, among which theremay be mentioned:

1) Their composition is often complicated and costly to achieve, notbecause of the usual cosmetic ingredients, but because of the nature ofthe milk-derived additives themselves, for example, pretreatmentsundergone by these, or the manner of extraction from the natural milk.

2) The storage duration at ambient temperature is often limited and thelevels of preservative agents (for example, alcohol) necessary for theirpreservation is often high, which may compromise, at least in part, theskin softening advantages which result from the presence of themilk-derived constituents.

3) The general aspect of the product is sometimes not very engaging, inparticular in regard to a lack of light reflection by the constituentsof the composition, a lack which must then be corrected by theincorporation of a pigment, in particular TiO₂. It is in effect evidentthat a product containing substances arising from milk should bring tomind, at first glance, by its appearance and by its colour, that itcontains, in effect, such substances.

4) Colour changes. Quite often cosmetic products containing milk have atendency to yellow with time and, because of this, become unsaleabledespite their unchanged intrinsic qualities.

For these various reasons, researches have been undertaken to bring tolight new compositions for cosmetic products containing milkderivatives, these compositions really having the appearance of milk orof mixtures containing milk, conserving well in storage, relativelysimple to formulate, and displaying, of course, all the recognisedadvantages of cosmetics formed on a milk base.

These researches have resulted in the products whose definition conformswith the attached claim 1.

It has in effect been observed, surprisingly, that starting from clearsolutions of sodium caseinate containing at least one surface-activeagent or surfactant, it was possible to obtain, by addition of calcium,in particular soluble salts such as CaCl₂ in the pH range indicated,stable milky solutions unmistakeably reminiscent of the appearance ofnatural milk. Such an operation in fact allows the reformation of milkprotein micelles, these being found in the form of calciumphosphocaseinate in a micellar and colloidal suspension. It isinteresting to note in this regard that in the absence of a surfactant,such an addition results rather in the precipitation of calciumphosphocaseinate.

The use of industrial casein, either pure or in conjunction with othermilk proteins (albumins, globulins, serum proteins) displays theadvantages of a product of an essentially constant nature, stable,relatively inexpensive, and practically free of lactose. The effects ofyellowing in storage and of alteration that are to be observed in thecase of cosmetics containing milk or milk products are in effect,principally due to lactose. It is thus possible, thanks to the use ofcasein, whose properties and nature remain invariable (.within certainlimits naturally), to provide cosmetics containing products derived frommilk whose composition and performance are stable from one manufacturingrun to another, which is extremely difficult to guarantee starting fromnatural milk.

The colloidal calcium phosphocaseinate solution which is in questionhere may be used to advantageously modify the majority of cosmeticproducts modifiable by the addition of milk or of ingredients derivedfrom milk and mentioned in the prior art. In particular, anon-exhaustive list of such products has been given with reference tothe document EP-A-46,326. However, the cosmetics which are preferredaccording to this invention are capillary (hair) products or those forbody use such as soaps, shampoos, lotions, creams, and bath products,etc. In a general manner, quantities of milk proteins (in the prescribedform) may be incorporated in such cosmetics and may attain 20% by weightwithout any major disadvantage in regard to colour, consistency, orstability in storage. Due to the use of purified casein, the addition ofgermicides and other biocides ma remain minimal.

Among the preferred products of the invention, there may be mentionedproducts for care of the skin and the hair, in particular products forshowers, baths, and shampoos, etc. Such products generally containsurface-active agents (anionic, cationic and non-ionic surfactants, ordetergent products), emolliants, and moisturizing agents (fattymaterials, fatty acids, protein constituents), biocides (germicides,bactericides. fungicides, etc.) perfumes, blueing agents, and opticalopalescents, opacifiers etc.

According to a preferred formula for a shampoo, for example, thiscontains by weight, the following ingredients: anionic surface-activeagents 10-50%, natural fatty acids 0.5-5%, milk-derived proteins 3-15%,calcium ion 0.1-1%, the remainder up to 100% being made up by the waterof the solution and at least one additional ingredient selected fromamong biocides, perfumes, blueing agents, opacifiers, opalescent andiridescent agents, and buffering agents. Preferably, the pH of such amixture is from 6.5 to 7, and its viscosity is from 3000 to 6000 cP.

Among the surface-active agents suitable for such a formulation, theremay be mentioned sodium and ammonium sulphates and sulphonates of fattyalcohols and of polyoxyalkylenes, for example, lauryl sodium sulphate orpolyoxyethylene glycol sodium sulphate. However, other surfactants mayalso suit, for example, non-ionic surfactants.

Among the natural fatty acids, there may be mentioned oleic acid,ricinoleic acid, myristic acid, linoleic acid, and stearic acid.

Among the biocides, there may be mentioned the salts of quaternaryamines, p-hydroxybenzoic esters, imidazolidinyl urea, phenoxyethanol,derivatives of isothiazolinone, formaldehyde, and benzoic, salicylic andsorbic acids.

To prepare cosmetics according to the present invention, one willadvantageously have recourse to the process defined in claim 6. It maybe noted that the term casein or soluble caseinate refers to eithersodium, potassium or ammonium caseinate, or acidic casein dissolved inan alkaline medium.

Thus, for example, in the case of the preparation of a shampoocomposition such as defined in claim 4, one may operate in the mannerdefined in claim 7. Preferably CaCl₂ is used as calcium salt, forexample, in the form of CaCl₂.2H₂ O; however, other water solublecalcium salts may also be used.

The Examples that follow illustrate the invention.

EXAMPLE 1: Preparation of a shampoo composition.

In 740 g of cold water, 72.1 g of sodium caseinate (AME-100, provided bythe Central Union of Swiss Milk Producers) were dispersed, then thismixture was heated to 70° C. in a homogeniser until completelydissolved. Then 120 g of sodium sulphate and of lauryl sulphate(Texapon - Z, supplied by Impag A. G., Zurich) and 24 g of oleic acidwere added to the solution.

The temperature was then reduced to 50° C., and 3 g of imidazolidinylurea and 5 g of phenoxyethyl p-hydroxybenzoate were added; then the pHwas adjusted to 6.75 by means of a 20% by weight aqueous KOH solution,and, with vigorous agitation and cooling, 20.5 g of an aqueous solutionof 64.8% by weight of CaCl₂.2H₂ O were added drop by drop.

The mixture changed from clear to a milky mass of an intense whitecolour, which was then perfumed by addition of 4 g of a perfume(Freezia, supplied by GIVAUDAN S. A., Geneva). This shampoo compositionwas tested by the usual means employed for cosmetics and demonstrated anexcellent washing power, while still preserving the hair and giving itan excellent gloss.

Storage tests for this shampoo at 40° C. have not shown any tendencytowards flocculation or separation of phases. At most a slight lesseningin light reflection has been observed, an effect which howeverdisappeared on cooling.

EXAMPLE 2: Preparation of a composition for baths.

The following ingredients were intimately mixed at 70° C. in ahomogeniser.

    ______________________________________                                        Ingredients           g                                                       ______________________________________                                        Water                 717                                                     Sodium caseinate (AME-100)                                                                          162                                                     Texapon-Z              78                                                     Oleic acid             38                                                     There was then added, at 50° C.                                                               5                                                      Phenonip (Nipa. GB)                                                           ______________________________________                                    

This mixture was called premix A.

A product for baths was then formed at 70° C. by successive addition ofthe following ingredients (% by weight).

    ______________________________________                                        Ingredients                %                                                  ______________________________________                                        Water                      6.32                                               SAG-10 (Silicone antifoam from                                                                           0.15                                               Union Carbide).                                                               Texapon-Z (Henkel)         8.87                                               Texapon-N (Henkel)         37.51                                              Neo-Purcellin-SE (0/W - 2/066280)                                                                        2.0                                                (emulsifier supplied by DRAGOCO, Germany)                                     Premix A                   35.0                                               Euperlan PK-771 (iridescent agent                                                                        3.0                                                supplied by Henkel, Germany)                                                  KOH (7.4% solution)        0.62                                               Then after cooling to about 50° C.,                                    there are then added:                                                         Phenonip - 100             0.2                                                Biopur - 100               0.2                                                CaCl.sub.2.2H.sub.s O (64.8% solution)                                                                   3.63                                               Perfume                    2.5                                                ______________________________________                                    

The whole was then homogenised at 7000 rpm for 5 mins., which yielded acomposition of pH 6.75.

By using the above product, whose appearance is of a constant milkywhite with iridescent reflections, in water, a very agreeable softeningbubble bath was obtained.

EXAMPLE 3: Preparation of a skin cream

In a mixer, 45.6 g of casein were dissolved in 548.8 g of water, thesolution was then brought to 70° C. and to it were added, whileagitating, 24 g of glycerol. This solution was identified as M-1.

In a mixer (Sovirel type SVS - 295), there were mixed at 70° C., 32 g ofCutina KD - 16 and 24 g of Lanette 0. Then, after 30 mins. of agitation,80 g of Cetiol V and 8 g of sweet almond oil were added. After agitationfor 15 mins. at 70° C., 5.6 g of anhydrous lanolin and 8 g of castor oilwere then added. This mix was identified as M-2.

While gently agitating at 70° C., the product M-2 was slowlyincorporated into the product M-1. The temperature was then lowered to50° C., and, while continuously agitating, there were successively added16 g of Hydroviton, 1 g of lactic acid, 2 ml of a 64.8% calcium chloridesolution, 0.8 g of Kathon CG, and 4 g of perfume. The temperature wasthen lowered to 40° C., and homogenisation at 7000 rpm for 5 mins. wascarried out.

A fluid revitalising cream was then obtained, allowing the skin to besoftened after a bath and it to be rendered supple and soft, while stillgiving an agreeable impression of freshness. This cream is suitable foreven the most sensitive skins.

We claim:
 1. A cosmetic or a soap product having the appearance ofnatural milk and comprising, other than the usual ingredients of such aproduct, a surface active agent and at least one substance derived frommilk, wherein this substance includes a member selected from the groupconsisting of casein, and a mixture of casein and other milk proteins,said casein containing no more than 0.1% of lactose, said casein beingpresent, at least in part, in the form of a colloidal and micellarsolution of calcium phosphocaseinate at a pH of from 6 to
 7. 2. Acosmetic product according to claim 1, characterised in that its contentof proteins of milk origin is from 3 to 20% by weight.
 3. A cosmeticproduct according to claim 1, characterised in that it consists of ashampoo containing, by weight: anionic surface-active agent 10-50%,oleic acid 0.5-4%, proteins derived from milk 3-15%, Ca⁺⁺ ion 0.1-1%,the remainder to 100% being formed of water and one or severaladditional ingredients selected from among biocides, perfumes, blueingagents, opacifiers, and buffering agents.
 4. A cosmetic productaccording to claim 3, characterised in that its viscosity at ambienttemperature is from 3000 to 6000 cP.
 5. A process for preparing acosmetic product according to claim 1, characterised in that at least apart of the usual constituent ingredients of the said product areincorporated in a homogeneous manner, these including at least asurface-active agent, a clear aqueous solution of casein or solublecaseinate optionally containing other proteins of milk origin, then asufficient quantity of calcium ions is added so that at pH 6-7 thesoluble caseinate is converted into a micellar colloid of calciumphosphocaseinate, then, if necessary, the remainder of the constituentingredients of the cosmetic are added.
 6. A process according to claim5, applied to the preparation of a shampoo according to claim 3,characterised in that all or part of the surface-active agent and of theoleic acid are mixed at a temperature of 50°-80° C. with an aqueoussolution of sodium caseinate, the greater part or all of the otheringredients with the exception of the Ca⁺⁺ ions are added, then, between40° and 60° C. and at a pH adjusted to a value between 6 and 7, aconcentrated aqueous solution of a water soluble calcium salt is slowlyadded, which converts the clear solution into a milky solution of highlight reflective power.
 7. A process according to claim 6, characterisedin that the calcium salt is calcium chloride.
 8. A cosmetic or a soapproduct having the appearance of natural milk and comprising, other thanthe usual ingredients of such a product, a surface active agent and atleast one substance derived from milk, wherein this substance includes amember selected from the group consisting of casein, and a mixture ofcasein and other milk proteins, said casein containing no more than 0.1%of lactose, said casein being present in an effective amount so as toresult in said appearance of natural milk and being present, at least inpart, in the form of a colloidal and micellar solution of calciumphosphocaseinate at a pH of from 6 to
 7. 9. A method for modifyingcosmetic products selected from the group consisting of products forcare of the skin and the hair, shampoos, dressings, hair lotions, bodylotions, cold cream, cleansing creams, emollients, detergents, soaps,make-up products, lipsticks, shaving products, sun screen products anddepilatories by giving them an appearance reminiscent of containingnatural milk, comprising the steps of incorporating to said cosmeticproducts at least one surface-active agent, soluble calcium salt and asubstance selected from the group consisting of casein, and a mixture ofcasein and other milk proteins, said casein containing no more than 0.1%of lactose, said casein being present in an effective amount so as toresult in said appearance of natural milk and being present, at least inpart, in the form of colloidal calcium phosphocaseinate at pH from 6 to7.